Composition of matter and method of making the same



OF MATTER AND METHOD MAKING THE SAME Walter-'1. Koenig, PhilaCOMPOSITION 2,108,893 PATENT OFFICE delphia, Pa., assignor toloane-Blabon Corporation, Philadelphia, Pa,

Delaware a corporation of No Drawing. Application SerlalNo.

7 Claims.

.This invention relates to a novel composition of matter to a novelmethod of making the same and to a novel method ofdrying oils andoleaginous compositions. More particularly, the invention relates to anoleaginous composition for coating, plastics and the like, especiallyadapted for use in the manufacture of floor covering materials, etc.,and to resinous products derived from said oleaginous compositions andto novel.

methods by which the oleaginous compositions are reacted to formresinous products, and particularly to the method of drying sucholeaginous compositions by resin-forming reactions.

This application is a continuation in part of my prior co-pendingapplication Serial No. 646,148, died September 7, 1932, entitledComposition of matter and method of making the same. In my said priorapplication, I have disclosed methods of drying oils by a resin-formingcondensation and a number of compositions suitable for drying by said.method and resulting from suchdrying. With similar objects in view tothose set forth in my said prior application.

I have now discovered that several condensing agents may be made toreact simultaneously or successively with the same oil, and that animprovement in quality likewise may be produced as compared with theproducts of condensing the 'oil and a single condensing reagent.

As will be apparent to those skilled in the art, there are infinitepossibilities for multiple condensations embodying the presentinvention. And by applying the general principles of organic synthesistogether with the principles and disclosures herein set forth, aninfinite variety of such combinations may actually be produced.

Some advantages may be secured by producing simultaneously differentcondensation products within the same mass, and thus there may beadvantage in using a plurality of condensing reagents, even though theymay mutually exclude each other from the oil molecules with which theyreact; but in the present invention, I am particularly concerned withcondensation products in which a plurality of condensing reagents arecondensed with the oil into the same molecule; and I believe that theimportant practical advantages are due to the'greater complexity of thecondensed molecule resulting from the attaching to the oil molecule oftwo or more diflerent molecules of the condensing reagents.

In many cases it is practicable to mix'the several condensing reagentswith the oil and to react them simultaneously. Where, however, onereagent has a tendency to condense with the oil molecule insuch a way asto exclude further condensation with the other reagent, I prefer toreact them successively, using first the reagent which is not exclusive.This successive procedure may also be preferable for other reasons, as,for

December 22, 1934, 758,864

(or. zoo-2) example, when the condensing reactions are preterablycarried on at diflerent temperatures or under diiferent conditions, orwhere one reacts with the oil so much more rapidly than the other that'a satisfactory condensation of the latter cannot be attained before theoil is set up. by

the former.

With China-wood oil, almost any two of the condensing reagents disclosedin my prior applications Serial Nos. 646,148 and 646,149, filedSeptember 7, 1932 now Patent Nos. 2,058,596 and 2,047,149 respectively,and in my co-pending applications Serial Nos. 758,859 to 758,863,inclusive, filed herewith may be used. Applications Serial Nos. 758,859and 758,861 are now Patent Nos. 2,058,597 and 2,058,598.

In my co-pending compounds have been described as giving the bestresults in the condensation reaction between the treated oil and thecondensing agent.

By cyclic organic compounds, I mean oxy-cyclic compounds which are truesaturated and true unsaturated oxy-heterocyclic compounds in which theelement is oxygen, and true oxy-carbocyclic compounds, having hydroxyl,keto, aldehyde or anhydride groups. Under cyclic organic compounds, Ialso include cyclic hydrocarbon terpenes.

By true saturated or true unsaturated oxyheterocyclic and trueoxy-carbocyclic compounds, I mean that the compounds consist of hydrogenand carbon atoms and the above-named oxygrcups. I include unsaturatedunsubstituted heterocyclic compounds in which the element is oxygen, assuch compounds will condense in accordance with my invention. It isunderstood that throughout the definitions supra, methyl groups, etc.,are included since they include only carbon and hydrogen.

With oils having fewer reactive linkages, should be taken to react theoil first with condensing reagents which combine with only one reactivelinkage of the oil, or under conditions such that condensation islimited to one such reactive linkage.

For example, I may charge parts by weight of China-wood oil, 10 parts byweight of phenol into a Bedford kettle and blow the mixture at about to200 F. until it forms a plastic solid when cooled.

Five parts of phthalic anhydride-are added to the resulting composition,and the mixture heated to about 280 F., preferably without furtherblowing, until the desired body is attained.

Upon cooling, a tough sticky plastic is produced which dries rapidly anduniformly at super-atmospheric temperatures to a tough, permanentlyflexible material which is highly resistant to alkalies and to abrasivewear.

Fillers, pigments, resins, etc., may be added care application, cyclicorganic during and/or after the cook, as, for example, is well known,and is common practice in linoleum manufacture as carried out prior tomy invention.

In case resins are added, I prefer to use synthetic resins as phenolformaldehyde or paracoumarone, instead of natural resins as rosin, etc.

Other oils, in which I include treated and untreated drying oils,treated semi-drying oils and non-drying oils, that possess double bondsin conjugate arrangement, e. g. -C=C--C=C or C=C-C==C-C=C-, (such asChina-wood oil, fish oils, oiticica oil, blown or properly oxidizedlinseed oil, blown or properly oxidized soya bean oil, blown or properlyoxidized poppyseed oil, etc., castor oil heated under reduced pressuresto form conjugate double bond structure and esterified, blown orproperly oxidized drying oil fatty acids, and the above treated anduntreated oils, having the above double bond conjugate structure, blownwith drying oil fatty acids or such oils to which blown or properlyoxidized fatty acids have been added), fall within the scope of myinvention. I prefer to use blown or properly oxidized oils, although theraw oils having the above described conjugate double bond arrangementwill dry in accordance with my invention.

Maleic anhydride and other anhydrides having similar reactive linkagesbetween C-atoms are, as set forth in my copending application Serial No.158,859 filed herewith, especially desirable for condensation with theoil, but because the condensation with the oil leaves the anhydridestructure free, the condensation tends to reduce thealkali resistance ofthe product. If, instead of the single condensation with the anhydride,a further condensation is effected with an oxycompound, e. g., analcohol, e. g., glycerol, a glycol, a hydroxy terpene, e. g., terpineol,ethylene glycol, or an ether such as anethol, which reacts with theanhydride structure, a product may be obtained which is much superior inalkali resistance.

As one example of this, Parts by weight heated to and held at atemperature of 280300 F. for 2 hours. The resulting product is a plasticsuitable for example for linoleum cement, and when dried. for a few daysin an ordinary linoleum heater it forms an excellent, tough, pliableresin.

A Bedford kettle may be used instead of a Walton kettle, and if themixture is blown, raw

oil may be used with as good results as the blown oil, and linseed oilwith almost as good results as China-wood oil. Thus, for example,

- Parts Linseed oil 200 China-wood oil 550 Maleic anhydride 225Glycerine 215 be followed by blowing to:

ing with the condensing reagents in a Walton kettle at 280 F. I

Other oils, as suggested above, may be used, resins, fillers, etc., maybe added, and the example may be varied in other ways, e. g., as

' already suggested in connection with the phthalic skilled in the artthat a feature of primary importance of the present invention. is thatthe reactions herein disclosed are capable of drying-the oils in filmswithout objectionable distortion whether the oil is extended upon asurface of large area or as an adhesive film on particles of a plasticcomposition. It constitutes, therefore,

.not only a method of obtaining novel resinous compositions, but evenmore important, a method of drying oils by converting them into suchresinous products. directly, and'after they have been given their formas finally desired.

It is of primary importance, moreover, that according to the presentinvention, the reaction can be initiated en masse and then interruptedat a point short of complete drying. Thus, the more costly final step ofheating the finished article can be reduced to a very short treatment.

In so far as this application relates to the condensation of cyclicanhydrides with oils, it is within the broad scope of my co-pendingapplication Serial No. 758,859 filed herewith.

In the examples given above, I have specified particularly plastics andprinting inks, since the invention gives very great advantages in thosefields. It is to be understood, however, that my invention is of muchwider application than the particular examples mentioned above and maybe applied generally to all sorts of protective and decorative coatingsand moldedor machine resinous products, including paints, enamels,varnishes and plastics such as would be used in floor coverings and thelike, printing ink, lithograph varnishes, coatings for tin cans, etc.,coating impregnating and insulating varnishes, pro-' tective coatingsfor automobiles, machinery, furniture and other articles, and plasticfor electrical insulation, chemically resistant articles, householdutensils, decorative objects, implements, handles, etc., to mention onlya few of the numerous applications of my invention.

In addition to the formation of the above type of condensation product,it is possible to produce another type whereby the two condensing agentswill react separately, at super-atmospheric temperatures at differentdouble bonds of the oil. Thus, mono-nuclear saturated true oxy-cycliccompounds, that will not react with each other under conditionsspecified, but that will separately condense with the oil, will react,in proportions depending upon afiinities, at different double bonds ofthe oil. As an example of this, cyclohexanone and cyclohexanol will notreact with each other under the conditions specified in the examplesgiven above, buteach will condense with the oil molecule at differentdouble bonds of the oil under the conditions specified. The same is trueof ary-alpha-keto-tetrahydronaphthalene and phenol. In fact, anymono-nuclear saturated true oxy-cyclic compound, as disclosed in mycopending application 646,148, will react similarly under conditionsdescribed above. Likewise this is true of phloroglucinol and resorcinol.

In either case, i. e., (A), where the condensation product of the oiland condensing agent reacts further with another condensing agent at theremaining reactive structure of the first condensing agent, or (B),where the two condensing agents will not react with each other under theconditions specified, but will separately condense with the oil atdifierent points of unsaturation in the oil molecule, a highly complexmolecule will result as a. final product which greatly increases thealkali resistance, flexibility, durability, appearance, etc., of theresulting resinous product. These features are especially desirable whenthe sheetedproduct is used .as a linoleum or similar material.

It seems clear that a condensation occurs. The extent of condensationdepends on the condensing agents used, but regardless whether thecondensation is partial or practically complete, the reaction fallswithin the scope of this invention, since my invention embraces rapiddrying action at super-atmospheric temperatures in substantiallynon-oxidizing atmospheres, as due to the condensation. In the case ofpartial condensation, 1. e., where the amount of condensing agent isless than in stoichometric relations, it is my theory that the presenceof the particular type of condensation product of the oil and condensingagents is responsible for the rapid drying. The

invention described herein cannot be construed in the same light as theaction of driers, as the action proceeds unimpeded or rapidly, as thecase may be, in substantially non-oxidizing atmospheres atsuper-atmospheric temperatures with definite favorable results startingas low as 120 E, which, in addition, difierentiates from polymerizationand oxidation under similar conditions.

If more than one condensing agent is used, it is not necessary to addthe several condensing agents as a mixture at the start of the reaction.The reaction may be started with a single condensing agent, and afterthe reaction has progressed to any point before becoming a solid mass,the reaction may be retarded by merely cooling the mixture. Additionalcondensing agent may then be added, if desired, and the reactionaccelerated again by merely raising the temperature. The addition ofmore than one condensing agent tends to create final products havingmore complex structures, thereby creating a tougher film in the finalproduct. It is understood that the reaction may be retarded andaccelerated any number of times before completion, and, if desired,additional condensing agent may be added which enter the condensationreaction. If desired, an additional quantity of the original condensingagentor a mixture of the original and a difierent type of condensingagent may be added. It is within the scope of this invention to includethe addition of an additional quantity of the same condensing agentusedat the start of the reaction and/or a different one at any point in thereaction. The feature of accelerating and retarding the reaction at anydesired point in the reaction is a very desirable point, and isaccompllshed by merely controlling the temperature. It is not necessaryto add additional condensing agentsto again accelerate the reactionafter it has been retarded, although this may be done if so desired, asexplained above.

In the above specification, I have given exampies and suggested certainmodifications for the purpose of illustrating the invention without inany way attempting to exhaustively cover all of the variousmodifications and applications of my invention. Similarly, I haveexpressed certain theories which I have developed in the course of myinvestigations and practical experience with this invention, which, Ibelieve, may be helpful to those who subsequently apply and extend theapplication of my invention. However, I have .not as yet tested thesetheories sumciently to set them up as certainly correct, and since theinvention is in no way dependent upon the correctness of anytheories-which I have expressed, it is to be understood that the scopeof my invention and of this application is not to be limited thereby. p

I have used the term condensation herein broadly to mean the union, oftwo or more organic substances with or without t e elimination ofcomponent elements.

What I claim is:

1. The method of hardening drying oil which comprises condensing amixture at super-atmospheric temperature in which the condensationreactants consist of oxidized drying oil having double bonds inconjugate arrangement and a plurality of different cyclic organiccompounds, said oil condensing with one of the cyclic organic compoundsto form a condensation product, then adding a difierent cyclic organiccompound and condensing the condensation product with the added cyclicorganic compound, thereby producing a complex molecule and a toughdurable mass.

2. The method of hardening drying oil as described in claim 1, in whicha synthetic resin is present in the mixture during the condensationreaction.

3. The method oi hardening drying oil as described in claim 1, in whichthe first cyclic organic compound to condense with the oil is maleicanhydride, and the second organic compound to condense is terpineol. Y

The method of hardening drying oil as described in claim 1, in which theone cyclic organic compound to condense with the oxidized oil isphthalic anhydride, and the second cyclic organic compound is a phenol.

5. The method of hardening drying oil which" comprises condensing amixture at super-atmospheric temperature in which the condensationreactants consist of omdized drying oil having double bonds in conjugatearrangement and a plurality of difierent cyclic organic compounds, saidoil condensing with one of the cyclic organic compounds to form acondensation product, then adding a different cyclic organic compoundand condensing the condensation product with the added cyclic organiccompound until the desired viscosity is obtained, cooling the condensedmixture and shaping the cooled condensed mixture into a desired usefulproduct, finally hardening the shaped product at super-atmospherictemperature.

6. The method of hardening drying oil as described in claim 5 in whichthe final hardening is carried on in an atmosphere substantially devoidof oxygen.

'7. The method of hardening drying oil as described in claim 5 in whichthe final hardening ocours in a substantial atmosphere of non-oxidizinggases given 05 by the shaped product.

